ChemInform Abstract: Metal Complexes with S4N4 Ligands: The Structures of Two Complexes of the Composition (TiCl4(S4N4))2.

Abstract

ChemInform Abstract Using the diffusion technique TiCl4 is slowly treated with S4N4 in CH2Cl2/CCl4 to yield a mixture of the title isomers. The orange-yellow α-isomer (III) crystallizes in the monoclinic system, space group P21/n with Z=2, whereas the red-brown β-isomer IV) belongs to the monoclinic space group P21/c with Z=4.

Ring‐shaped [(TiCl2)(1,3‐P2S8)]2 Molecules Containing Uncommon [P2S8]2– Anions

“…This is certainly due to the rigid bite angle of the thiophosphate groups, which exhibit bond angles S-P-S close to the ideal tetrahedral angle, see Table 4. The axial bond angles of the octahedron are 159.7°(S3-Ti1-S7), 166.9°(S2-Ti1-Cl2), and 166.4°(S8-Ti1-Cl1), respectively, and demonstrate the deviation from the ideal octahedral surrounding of Ti 4+ An alternate description of this dimeric molecule is the condensation of two TiS 4 Cl 2 octahedra through two edges formed by sulfur with PS 4 tetrahedra. Two of these tetrahedra share one vertex and are additionally linked by a sulfur atom connecting the fourth vertex, see Figure 3.…”

“…The octahedra TiS 4 Cl 2 are quite distorted, exhibiting angles S-Ti-S of 79.6°and 79.8°respectively, and angles Cl-Ti-Cl of 95.3°, far away from an ideal 90°angle, see also Table 4. This is certainly due to the rigid bite angle of the thiophosphate groups, which exhibit bond angles S-P-S close to the ideal tetrahedral angle, see Table 4.…”

“…The formation of TiCl 4 adducts with Lewis-bases was observed before, and especially the cage-like S 4 N 4 molecule showed a variety of possibilities to connect with the metal chloride. For example, [(TiCl 4 )(S 4 N 4 )] 2 molecules have been observed and structurally characterized earlier [3,4]. Organophosphanes can also act as electron donors towards titanium, e.g., in [(TiCl 4 )(Ph 3 P)] or [(TiCl 4 )(Ph 3 PCh)] (Ch = O, S) [5,6].…”